Regulating Sodium Deposition Behavior via Polar Functional Group‐Based Interfacial Engineering on an Industrial‐Scale Anode for High‐Performance Na‐CO 2 Batteries

ABSTRACT The development of sodium‐carbon dioxide (Na‐CO 2 ) batteries is crucial for renewable energy utilization and CO 2 fixation. However, their practical application is severely hindered by Na dendrite formation coupled with aggressive CO 2 electro‐/chemical corrosion, and extremely low Na anode utilization rates. This study addresses these interconnected challenges by employing a multifunctional covalent organic framework (COF) coating. Specifically, the C 6 O 6 ‐TAPT COF features a fully conjugated skeleton for rapid electron cloud response, abundantly distributed sodiophilic chelation sites (C═O and C═N) for Na + capture, and ordered AB stacked structure for homogenizing Na + flux. The COMSOL simulations further demonstrate the stress‐regulating strategy in mitigate solid electrolyte interphase (SEI) cracking and separator puncturing risks. Consequently, Na‐CO 2 batteries using the designed industrial‐scale anode achieve low polarization (1.4 V) and sustain stable cycling for over 1100 h at 100 mA g −1 across 0–60 °C. Remarkably, it maintained over 100 cycles at reduced N/P of 10 and delivered a high discharge capacity of 11552 mAh g −1 under lean electrolyte conditions (8.7 µL mAh −1 ). This study validates stable and functionalized COF substrates with dendrite suppression capability in Na‐CO 2 batteries, proposing a scalable pathway with implications for next‐generation energy storage.